Production of new azo dyestuffs containing chromium



Patented Apr. 30. 1940 PRODUCTION O NEW Azo DYESTUFFSEV CONTAININGonnoMwM Hans Kaemmerer and Ludwig Neumann, Mannhelm, and RobertSchweizer, Ludwigsh'afen-on the-Rhine, Germany, assignorsl to General vAniline & Film Corporation, a corporation of Delaware 1 no Drawing.Application Ju 11, 1939, ,Serial No. 283,826. In Germany Jul znisss is(ll aims. (c1. zoo -151) The present invention relates to newazo dyestuffs containing chromium. r

We have found. that new azo dyestuffs containing chromium are obtainedbycoupling diazo compounds of arylamines containing a hydroxy tallizedsodium acetate is allowed to run in and or. alkoxy group inortho-positlon to theamino then a solution of 212 parts of anhydroussodium group with nitro. derivatives of 1-amino-8-hycarbonate is run inslowly. After several hours, droxy-naphthalene sulphonic acids andtreating. the dyestuff is formed; it is salted out in the the aimdyestuffs obtained with agents capable usual way. It dyeswool dark blueshades which I of yielding chromium. y l change to olive-green-brown byafterchr'oming on l The said nitro compounds are obtained by treatthefibre. v I ment of l-amino-8-hydrbxynaphthalene sulphon For thepreparation of the chromiumcompound ic acids with mixtures of nitricacid and sulin substance, the dyestuff isheated with a formic phuricacid. As diazo components there may be acid solution of 76 parts ofchromium oxide for T5 mentioned 1:amino-2ehydroxybenzenesorortho- 3hours under reflux at 100 C. The violet color.hydroxyaminonaphthalenes," as for example 1- gradually changes to green.The .dyestuil sepamino-2-hydroxybenzene, and in particular the aratedbysalting out yields on chrome and glace' halogen and nitro substitutionproducts derived leather deep green shades, of excellent fastnesstherefrom, and the l-amino -Z-alkoxy compounds properties. If thechroming be carried out under corresponding thereto. Diazo componentscone pressure at 133 (2., a dyestuff giving a blacktaining sulphonicacid groups may also be used. brown dyeing is obtained.

The new dyestuffsyield violet-blue dyeings on For the dyeing of chromeleather, the procedure wool from. an acid bath, the dyeings changing to'may for example be as follows: 10 grams of olive-green by.afterchroming. The chromium chrome calf leather are deacidifiedfor30'minutes compounds prepared in substance dye wool fast, with 1.5per cent borax solution and rinsed for usually yellow-green shades. Thenew dyestuifs about ill-minutes. The piece thus prepared is are ofspecial value for dyeing chrome and glac then brought into a dyebathprepared by disleather. Deep dyeings, usually of deep green solving0.1.g1 m 0 dyestuff 11 cubic centishades, are obtained thereon.Ascornparedwith et es o wa Dyeing is ed for 20 mini the correspondingdyestuffs with 1-amino-8-hyutes neutral at 60 C. while continuallymoving 39 droxynaphthalene sulphonic acids free from nithe bath. It is.then fatted with neats-foot oil tro groups, the new dyestuffs have theadvantage or another grease usua Ort pu p se. It is that they are stableto mineral acidst Moreover hendyed for another minutes rinsed for a, thenitro groups effect an increase in the color short time, stretched anddried. In order to rein 5 strength and a displacement of the shadetowards der the leather supp it is brought to mo st yellow, so thatquite new shades of color are ob- Sawdust for hillils, then Pe ed outand tained. The new dyestuffs have a very good fast- Stretched until its y. gglal shing and light and an excellent level- Example l The complexchromium compoundsmay be The diazo compound of 199 parts of Z-aminoif)pared in substance'according to usual methods is coupled in the byheating the dyestuffs with compound f trj. manner described inExample 1. with 284 parts valent chromium with or without pressure; of*m y u The following examples will further illustrate phomc acld(prepared by mtmting m 3 how this invention may be carried outinprachydroxynaphthfflenef4'Su1phonic acid in concentice but theinvention is not restricted to these mated sulpbunc aclm' The fi giveson examples The parts are by weightunless othelu wool dull violet shadeswhich change to olivee ifi d .green by afterchroming on the fibre.

Example 1 d The chromium compound of the dyestuff, obtained by treatingwith a formic or sulphuric acid 125 parts of 34.5 per cent caustic sodasolution solution of 76 parts of chromiumoxidebetwecn 100 which havefirst been diluted with water are added and 133 C., yieldson wool and onleather deep to 284 parts ,of 1-amino-7-nitro-8-hydroxynaphgreen,uniform shades which are fast to acids, thalene-5-sulphonic acid(obtained by nitrating light andwashing. 5 commercial l-amino 8hydroxynaphthalene-5- sulphonic acid in concentrated sulphuric acid);

the diazocompound of 199 parts of 2-amino-4.6- dinitro:l-hydroxybenzene,prepared in, known manner, is added, a solution of 272 parts of crys-ABy using the nitro compound of 1-amino-8- fast, clear green shades.

' Example 3 The dmzo compound of 199 parts of z-ammofly hours underreflux with a formic acid solution of 80 .parts of chromium formate.

4.6-dinitro-l-hydroxybenzene is coupled in the manner described inExample 1 with284 parts of 1-amino-5-nitro-8-hydroxynaphthalene '7sulphonic acid (obtainable by nitration of the '1-'aminc-S-hydroxynaphthalene 7 sulphonic acid which is obtainableaccording to the German specification No. 82,900). 'I'hedyestuff may beconverted into the chromium compound] by heating with salts'of trivalentchromium with or without pressure in the manner described in theforegoing examples. The dyeings on leather and on wool are deep greenand have good tinctorial properties.,; 3 I

,---Dyeings n glac leather may be produced'for example in the followingmanner: 5 grams of chromed glac leather are deacidified with 1-5 percentborax solution, rinsed for 5 minutes and 'brought.intoadyebathcontaining 0.25 gram of dy estuff in [100 grams of water. It is thendyed forffrom 1 to 2 hours" at C. without additions, while continuallymoving the. bath, until the". leather is dyed through. It is then fattedwith egg yolk and further worked for 30 minutes. 5 percent of acetic orformic acid are then added and the leather again dyed for,30 minutessFinally lper'centof chromium acetate is added and the dyeing continuedfor an hour. The

leather is' then rinsed for a short time, stretched, dried, treatedwith' sawdust, pegged out and again dried.

. Example 4 154 parts of 4-nitro-2-amino-l-hydroxybenzene are diazotizedin known manner and the azo dyestuff is prepared in the manner describedin Example 1 with 284 parts of 1-amino-7-nitro-8-hydroxynaphthalene=4-sulphonic acid.

i If the dyestuff be treated while hot with chromium formate, a chromiumcompound is obtained which dyes chrome leather dark green shades fast towashing.

' Example 5 The diazo compound prepared from 188.5 parts of-chlor-G-nitro-2-amino- 1-hydroxyblenzene is coupled in the mannerdescribed in Example 1 with 234 parts of1-amino-7-nitro-8hydroxynaphthalene-l-sulphonic acid. The dyestuffformedis isolated and heated for 3 hours at 130 C. with a formic acidsolution of 80 parts of chromium oxide. The complex chromium compoundofthe dyestufi is salted out and dried. It dyes glac leather deep. greenfast shades.

' Similar dyestuffs are obtained by using under otherwise identicalconditions the diazo compounds prepared from fi-chlor-i-nitro-fi-aminol-hydroxybenzene or from 4-chlor-5-nitro-2-aminolehydroxybenzene.

- nitro group.

Example 6 From the solution' thus obtained the formic acid is distilledoff. The solid dyestuff obtained dyes chrome and glac leather dark greenshades which are fast to washing and to acids.

What we'claim isz 1. Complex chromium compounds of azo dyestuifs of thefollowing formula A-N=NB wherein A stands for an aromatic radicleselected from the benzene and naphthalene series containging ahydroxygroup in ortho-position to the azo group shown, and wherein B stands forthe radicle of a 1-amino-8hydroxynaphthalene sulphonic acid containing anitro group. 2. Complex chromium compounds of azo dyestuffs of thefollowing formula A-N=N---'B wherein A stands for amonocyclic radicle ofthe benzene series containing a hydroxy group in ortho-position totheazo group shown, and wherein B stands for'theradicle of a1-amino-8-'-- hydroxynaphthalene sulphonic acid containing a" 3. Complexchromium compounds of azodyestuffs of the following formula A-N'=N+B'wherein A'stands for a monocyclic radicle of the benzene seriescontaining at least one nitro group and containing a hydroxy group inortho-position to the azo group shown, and wherein B stands for theradicle of a 1-amino-8-hydroxynaphthalene sulphonic acid containinganitro group.

4. Complex chromium compounds of'azo dyestuffs of the following formulaA-N=NB v 4 wherein A stands for a monocyclic radicle of the benzeneseries containing at least'one nitro group and containing a hydroxy'group in ortho-position to the azo group shown, and wherein B stands forthe radicle of l -amino-7-nitro-8-hy- 4 droxynaphthalene-5-sulphonicacid. 5. Complex chromium compounds of azo dyestuffs of the followingformula AN=NB' wherein A stands for a monocyclic radicle of the benzeneseries containing at least one nitro group 5 and containing a hydroXygroup in 'ortho-position to the azo group shown, and wherein B standsfor the radicle of 1-amino-7nitro-8-hydroxy-"naphthalene-4-sulphonicacid. I 6. Complex chromium compounds of azodyestuffs of the following formula A--N=N--B- wherein A stands for amonocyclic radicle of the. benzene series containing at least one nitrogroupand containing a hydroxy group in ortho-posi tion to the azo groupshown, and wherein B stands for the radicle of1-amino-5-nitro-8whydroxy-: naphthalene-'Z-sulphonic acid.

- I-IANSKAEMMERER.

LUDWIG NEUMANN. ROBERT SCI-IWEIZER.

